Hydrodesulfurizing a highly olefinic gasoline containing cyclic sulfur compounds



United States Patent HYDRODESULFURIZING A HIGEHJY OLEFHNIC GASOLINE CONTAINING CYCLEQ SULFUR COMPOUNDS Edwin S. Johanson, Trenton, N. .L, assignor to Hydrocarbon Research, Inc, New York, N. Y., a corporation of New Jersey No Drawing. Application May 16, 1952, Serial No. 288,337

16 Claims. (Ci. l9628) This invention relates to the treatment of hydrocarbon oils and is more particularly concerned with the treatment of a raw cracked gasoline fraction. The invention is concerned primarily with the treatment of raw cracked gasoline fractions to produce a finished gasoline of commercially acceptable sulfur content, storage stability and octane number.

At the present time it is desirable that commercially acceptable motor gasoline have a sulfur content of not greater than 0.3% by weight and preferably not greater than 0.1%, as measured in accordance with ASTM methods D129-49 and D90-47T. Specifications for commercial motor gasoline likewise require that it pass an existent gum test, in accordance with ASTM method D381, in which the gasoline must show less than 5 mg. of gum per 100 ml. In addition, it is highlydes-irable that commercial motor gasoline meet the storage stability requirements set forth in ASTM methods D910-48T or D525-49. Finally, the demands of modern high compression engines make necessary the production of motor gasoline possessing a high octane rating, usually determined as clear research octane number in accordance with ASTM method D90848-T. Arithmetic averages in January .1952, for motor gasoline sold in 45 U. S. cities indicate research octane ratings of 83.2 and 90.0 for regular and premium gasolines, respectively, with such gasolines containing an average of 1.35 and 1.75 cc./ga l., respectively, of tetraethyl lead. I

In modern petroleum refining practice, his highly advantageous to convert part or all of the higher boiling fractions of the crude oil to materials boiling in the gasoline range. This is effected by processes which involve the cracking of the higher boiling hydrocarbons into hydrocarbons boiling in the gasoline range. However, in many cases, the gasoline fraction which is produced by cracking (hereinafter referred to as raw gasoline) requires further processing to provide a commercially acceptable producthaving a sulfur content, storage stability and octane number within the above specified limits. Various processes have been proposed for treating such raw gasoline fractions to bring them within the desired specification limits, and some of these processes have been commercially used with varying effectiveness.

While sulfur compounds are found in varying amounts in petroleum crudes or fractions, the amount of such compounds often exceeds a value corresponding to 1.0% by weight of sulfur. When such a crude or crude fraction is cracked, the raw gasoline product thereby obtained does not meet the above limits with respect to sulfur content. Furthermore, the sulfur compounds in the raw gasoline often exist as thiophenes and compounds of similar cyclic structure. Such cracked raw gasolines are generally of moderate to high octane number, containing to 50% by volume of aromatic hydrocarbons and at least 20% by volume of olefins, and all known methods for removing cyclic sulfur compounds bring about the destruction or conversion of some of these unsaturated hydrocarbons. For example, when hydrogenation at relatively high pressures and relatively low temperatures is 2,774,719 ?atented Dec. 18, 1%56 ice employed, the olefins present in the cracked gasoline are completely hydrogenated to parafiins, i. e.

It is well known that such paraffins have clear research octane numbers which are as much as 40 octane numbers lower than the corresponding olefins from which they were formed. Thus, such treatment of a raw cracked gasoline fraction produces a finished gasoline which is generally of appreciably lower clear research octane number than the raw gasoline, and which is in all cases of lower clear research octane number than would have been obtained if said olefins had not been hydrogenated. Where the cracking operation produces a raw gasoline which satisfies octane number requirements without the addition of tetraethyl lead, e. g., above 8:3 clear research octane number, such utilization of conventional hydrogenation treatment to remove cyclic sulfur compounds results in a finished gasoline which is of considerably reduced clear octane number [and which consequently requires significant quantities of anti-knock additives to achieve octane requirements. Thus, the principal problem which these cracked raw gasoline fractions of high octane number and high sulfur content present is the reduction of sulfur content'to commercially acceptable limits without adverse effect upon the clear research octane number. Similarly, when such cracked raw gasoline fractions are relatively unstable, it is necessary to increase their stability to the desired extent without adverse elfect upon the other properties of the gasoline. These are problems which have not been solved in a satisfactory and eificient rrranner by prior processes for treating raw gasoline.

A principal object of the present invention is to provide a process for treating raw gasoline fractions containing at least 20% by volume of olefins and more than 011% by weight of sulfur as thiophenic or other cyclic sulfur compounds, which process will eliminate a substantial portion of said sulfur compounds, while maintaining the major portion of said olefins.

It is a further important object to provide .a process for treating said raw gasoline fractions, which will eliminate a substantial portion of said sulfur compounds, while increasing or at least maintaining the clear research octane ratings of said raw gasolines.

It is another object of the invention to provide a process of the character indicated which is also elfective simultaneously to increase the stability of such raw gasoline fractions.

Still another object is to provide an improved cracked raw gasoline treating process which avoids the shortcomings of treating processes heretofore proposed.

It is a feature of the invention that cracked raw gasoline is treated at an elevated temperature and at a predetermined hydrogen partial pressure in the presenc'e oif a material having catalytic activity such that the objectionable cyclic sulfur bodies are converted into readily separable forms, and bodies which render the gasoline unstable are converted to more stable forms, without significantly decreasing the clear research octane number of the raw cracked gasoline, even when the octane number exceeds 80. In many cases, the process of this invention increases the octane number. Thus, the application of the process to raw gasolines of clear research octane number exceeding makes it possible to meet commercial octane requirements without the addition of anti-knock agents.

In accordance with the invention, a cracked raw gasoline fraction containing over 011% by weight of sulfur a temperature of 775 to 925 F., preferably at a temperature of about 800 to 900 F., in contact with particulate material of the character hereinbelow described. The total pressure in the treating Zone and the introduction of hydrogen and raw gasoline are controlled in known manner to provide a hydrogen partial pressure of 20 to 1 p. s. i. (pounds per square inch), preferably 30 to 70 p. s. i. The total pressure of the system may vary over a relatively wide range, but it is generally preferred to use a total pressure not exceeding about 400 p. s. i. g. (pounds per square inch gage).

The particulate contact material employed in the treating zone is a siliceous catalyst of the type which has been employed for cracking hydrocarbons, containing a catalytic promoter comprising a metallic element of group VA, group VIA or group VIII of the periodic table. The metallic elements of group VA are V, Ob and Ta, and those of group VIA are Cr, Mo, W and U.

Typical suitable siliceous catalysts are acid-treated clays, heat-treated montmorillonite, and natural and synthetic silicates containing some hydrogen atoms which are relatively mobile.

It is today generally accepted that a certain acidic nature is essential for the effectiveness of catalysts for cracking of high molecular hydrocarbons to lower molecular fragments, for isomerization of parafiins and olefins of relatively low octane number to corresponding compounds of higher octane number and for other reactions desired in the refining of petroleum hydrocarbons. This same acidic nature is apparently also essential to the siliceous catalysts used in the process of this invention.

A class of catalysts with the proper acidic nature which can be used in accordance with the present invention is that of solid particles containing silica and such amounts of diflicultly reducible metal oxides that the molecular ratio of silica to the other oxides exceeds appreciably the value of 1. As all these combinations of silica with other oxides, such as for instance, alumina, zirconia, titania, chromium oxide, magnesium oxide and others, contain small amounts of water, it is quite likely that the solid phase comprises a kind of complex acid in which some hydrogen atoms are in a rather mobile state especially at the surface of the solid particles. This view and experimental support for it have been presented by R. C. Hansford in a paper entitled, A Mechanism of Catalytic Cracking, Ind. and Eng. Chem., 39, 849 (1947). The specific catalyst mentioned in this paper was composed of approximately 12% alumina and 88% by weight silica (on dry basis). In another paper entitled, Montmorillonite Cracking Catalyst, Ind. and Eng. Chem, 41, 1845 (1949), Alexander Grenall has demonstrated the presence of hydrogen ion in Filtrol clay catalysts.

Silica gels which have been impregnated, even with as little as 1% alumina, have been shown to be efficient catalysts for cracking by Pitzer in Advancing Fronts in Chemistry, vol. 1, page 33, 1945, Rheinhold Publishing Corp. Another catalyst has been described by OKelly et al. in Ind. and Eng. Chern, 39, 154 (1947), as being prepared by the co-precipitation of the hydrous oxides of silicon and aluminum in a weight ratio of 9:1 of silica to alumina. A tri-component catalyst consisting of silica, alumina and zirconia has been described by Thomas et al. in J. Am. Chem. Soc., 66, 1694 (1944).

Suitable catalysts can be prepared by using natural clays as a starting material. Many clays contain silica and alumina in a ratio which corresponds to the postulate that the number of moles of silica exceed appreciably the number of moles of alumina or other oxide. However, some of these clays contain, instead of mobile hydrogen atoms combined with excess silica, otheratoms, such as alkali and alkaline earth atoms. Such clays can be activated by removing part or all of the alkali and alkaline earth atoms and replacing them with hydrogen atoms by treatment with acid. Other clays, which already in their original composition have a potential acidic nature by having the proper ratio of silica to alumina or other oxides, can be activated by heat treatment (cf. Alexander Grenall l. c.).

All of the aforementioned natural and synthetic materials are efiective siliceous catalysts for the purposes of this invention. To recapitulate, the siliceous catalyst is a combination of a major weight proportion of silica and a minor weight proportion of one or more difiicultly reducible metal oxides, preferably aluminum oxide; this combination may be effected synthetically or it may be derived from natural materials like clays through activation by heat and/ or acid treatment. It is observed that the siliceous catalysts of this invention are materials which can generally be classed as natural or synthetic silicates, aluminum silicates being prominent in this classification.

Examples of particularly suitable catalytic promoters comprise molybdenum, chromium, tungsten, cobalt, vanadium, platinum and nickel. Two or more catalytic promoters may be used at the same time; the use of cobalt and molybdenum together, for example, gives excellent results. The promoters are conveniently incorporated with the siliceous catalysts as oxides or sulfides by known methods of preparation involving impregnation, precipitation or co-precipitation. These oxides or sulfides are partially or completely reduced by hydrogen to their most active form. This reduction may take place in the reaction zone itself or may be effected by preliminary exposure to hydrogen or hydrogen-containing gas. The efiective promoter may thus comprise a metallic element of the above-specified groups in the form of an oxide, a sulfide or as the elemental metal.

In the process of this invention, while substantially pure hydrogen is advantageously used, a gas mixture containing hydrogen and inert gases, such as nitrogen or methane, may be employed with efficacy. In the latter case it is preferable to use a gas mixture having at least about 30% by volume of hydrogen in order to avoid the necessity of passing excessively large amounts of gas through the reaction zone to provide the desired hydrogen partial pressure of 20 to 100 p. -s. i. and in order to avoid the necessity of raising the total pressure of the system to a high value.

The term gasoline fraction as herein used has its conventional meaning, viz., a hydrocarbon fraction boil ing within the temperature range of 90 to 400 F., although it will be apparent that the treating process of this invention is applicable to hydrocarbon fractions in which material boiling within the gasoline range comprises the predominant portion of the fraction.

Cracked raw gasoline fractions from various sources are advantageously treated in accordance with the process of the invention but the improved process is of particular value, as already mentioned, in reducing the sulfur content of cracked raw gasoline fractions of rela- ,tively high octane number, e. g., clear research octane numbers of at least about 80, and more particularly between and 90, containing substantial quantities of mono-olefins, such as gasoline fractions produced by the process described and claimed in the copending application of Percival C. Keith, Serial No. 139,758, filed January 20, 1950, now U. S. Patent 2,606,862. As previously mentioned, the present process is effective to remove even large proportions of sulfur bodies, including thiophenes and similar cyclic compounds, without any appreciable adverse efiect upon the high octane number of the raw gasoline. In some cases the octane number is essentially unaffected, i. e., it is not changed by more than one or two units, whereas in other cases it is even increased by a substantial extent.

In the process described in the above-mentioned Keith application, a crude hydrocarbon oil, particularly a heavy residual product, is cracked at a temperature of 800 to 1050 F. and at a total pressure of 200 to 800 p. s. i. g. in the presence of a particulate contact material and .material.

. n V the regeneration product gases produced by treating spent contact material contaminated with carbonaceous material at a temperature of about 1600 to 2500 F. with steam and oxygen of at least 90% by volume purity. The hydrocarbon etfiuent from that process is fractionated to yield a cracked raw gasoline which may suitably be treated by the process of this invention.

The invention is, however, not limited to cracked raw gasoline fractions produced in any particular manner but is applicable to any cracked raw gasoline having at least 20% by volume of olefins, and thus a clear research octane number greater than that of a virgin naphtha, e. g., above about 40. The present process is of particular effectiveness, however, on those cracked raw gasoline fractions having an exceptionally high olefin content, c. g., of the order of 30% by volume or higher, and high clear research octane numbers of the order of 80 to 90.

A typical raw gasoline produced by the process of the above-mentioned Keith application has a relatively high octane number, e. g., a clear research octane number of about 90, and contains a high proportion of olefins. Such a raw gasoline generally has, however, a substantial amount of diolefins which tend to render the gasoline unstable, as by depositing gums on standing, and when the gasoline has been derived from a crude oil of very high sulfur content, the raw gasoline generally has a substantial quantity of cyclic sulfur compounds such as thiophenes. For example, a Boscan (Venezuelan) crude is characterized by a very high sulfur content of the order of 5% by weight and, when cracked, the resulting .raw gasoline will contain about 1.5% by weight or.more

of sulfur. Thus, although the sulfur content has been reduced, it has not been sufficiently reducedto meet commercial motor gasoline specifications. Cracked raw gasoline fractions to which the present process is of particular application, such as gasoline produced in accordance with the above-mentioned Keith procedure,'will generally have the following approximatecomposition (percent by volume) .Without tying the invention to any particular theory of operation, the process appears to involve the following types of reactions which take place more or less .simultaneously. Thiophenes and related cyclic sulfur compounds are converted to normally gaseous sulfur compoundslike hydrogen sulfide, and diolefins areconverted to mono-olefins with the formation of some polymeric At the same time, aromatic hydrocarbons are not affected and only mild hydrogenation of mono-olefins takes place so that the excellent anti-knock properties of the raw gasoline are not impaired. In addition, dehydrogenation of naphthenes is facilitated by the conditions employed, resulting in the formation of additional quantities of aromatic compounds of excellent anti-knock characteristics. Cracking reactions also occur and these reactions maintain the octane number of the gasoline at ahigh levelwithout excessive degradation of the gasoline to less valuable gaseous products. The catalysts employed, containing relatively mobile hydrogen atoms, likewise promote isomerization reactions which also assure a relatively high octane number in the finished gasoline.

The raw gasoline treating process is suitably carried out in conventional gasoline treating apparatus wherein, in accordance with the invention, the raw gasolineis introduced into a reaction zone in contact with particulate catalytically promoted catalyst. The apparatus shown in the above mentioned Keithapplication may be employed,

preferably the process is carried out in a fluidized bed such aslis used commercially in the catalytic cracking er hydrocarbon oils, the hydrogen or hydrogen-containing gas being advantageously employed as the fluidizing medium. The contact material is continuously or intermittently withdrawn from the treating zone and regenerated in any convenient manner, as by treating it at elevated temperature with oxygen or air and, if desired, other gaseous materials such as steam.

The particular apparatus used for the process and the particular method of regenerating the catalyst form no part .of the present invention and any convenient apparatus and method of catalyst regeneration may be employed. In regenerating the catalyst care must be taken, however, in accordance with commercial regeneration techniques, to avoid the use of temperatures which destroy or adversely affect the catalyst. In the regeneration of the promoted catalyst of the present process, temperatures in excess of 1200 F. are generally to be avoided.

In order to facilitate the maintenance of the desired temperature in the reaction zone, the raw cracked gasoline to be treated is advantageously preheated to a temperature of 400 to 800 F., preferably about 500 to 700 F., before being fed into the reaction zone. At such temperatures the gasoline is at least partially vaporized. The hydrogen or hydrogen-containing gas may also be preheated to about the same temperature as the gasoline.

Treatment of the cracked raw gasoline in the reaction zone under the specified conditions is carried out to an extent sutficient to reduce the sulfur content of the raw gasoline and to impove its stability to the desired degree. 'Advantageously, the desired reaction is insured by employing a raw gasoline feed rate in the range of 0.5 to 5, preferably 0.5 to 1.5, volumes of liquid per hour per volume of catalyst, while employing a hydrogen flow rate of 500 to 2500 standard cubic feet (calculated as pure r hydrogen) per barrel of raw gasoline fed.

The efiluent from the treating zone will contain vapors of the hydrocarbons within the gasoline range admixed with a small amount of higher boiling hydrocarbons formed by polymerization and/ or condensation in the reaction zone, and with more volatile compounds including readily removable sulfur compounds formed by the breakdown of thiophenes and like refractory sulfur compounds in the reaction zone. The effluent is fractionally vdistilled to separate the desired gasoline fraction from the other constituents.

The finished gasoline fraction thus produced is of low sulfur content, high stability and high octane number and meets the specifications for commercial motor gasoline notwithstanding the presence of a substantial quantity of sulfur compounds and diolefins originally in the cracked raw gasoline. The sulfur content of the finished gasoline can be reduced to below 0.1% by weight by the present process, as well as below the 0.3% by weight level presently accepted for marketable motor gasoline.

For a further understanding of the invention, reference is made to the following specific example which is intended as illustrative of the process without, however, being intended as limitative thereof.

The cracked raw gasoline which is treated was obtained from a heavy hydrocarbon oil which was subjected to cracking in accordance with the aforesaid Keith process at a temperature of about 900 F. in the presence of the regeneration gases resulting from the decomposition of the carbonaceous residue on the particulate carrier with steam and oxygen of by volume purity at a temperature of about 1700 F. The efiluent from the cracking operation was condensed and fractionally distilled to separate the raw gasoline fraction which has a 400 F. end point and has the following characteristics:

Total sulfur, weight percent (ASTM-Dl29-49)- 1.90 Sulfur as thiophenes, weight percent 1 3 In accordance with the present invention, this raw gasoline is heated, as by passing through the coils of a tube still, to a temperature of about 700 F. The gasoline is then discharged into a reaction zone containing fluidized particles of a molybdenum promoted commercial silicaalumina cracking catalyst prepared by co-precipitation of the hydrous oxides in the ratio of about 9:1 by weight of silica to alumina followed by impregnation with molybdenum nitrate, drying and calcining in the usual manner.

reaction zone, the temperature is maintained at 825 F.

and the total pressure is maintained at 90 pounds per square inch gage. The heated raw gasoline is introduced at a rate to provide a space velocity of 1.0 volume of liquid gasoline per hour per volume of catalyst in the reaction zone and the hydrogen is introduced at a rate to provide a hydrogen partial pressure of 70 pounds per square inch.

The gasiform efiluent is continuously removed from the top of the reaction zone, condensed, and then subjected to fractional distillation to separate from the gasoline more volatile hydrocarbons and gases, and particles which may have been carried over with the effluent, and a small proportion of higher boiling hydrocarbons formed in the reaction zone. By the foregoing treatment the above-identified raw gasoline fraction is converted into a finished gasoline fraction having the following characteristics Total sulfur, Wt. percent (ASTM-Dl29-49) 0.20 Octane number, CFRR clear (ASTMD90848T) 87 Bromine number, cg./ gm. (ASTMD87546) 40 Olefin content, vol. percent 27 Copper dish gum, mg./ 100 ml. (ASTMD910 4ST) less than 10 Existent gum, mg./100 ml. (ASTM-D38l- 49) less than The yield of gasoline is 83.7% by volume of charge, and the total yield of liquid products is 89.9% by volume of charge.

It will be seen from the foregoing example that, in accordance with the process therein described, a cracked 'raw gasoline having a high content of sulfur as thiophenes and high in gum-forming constituents is converted to a finished gasoline containing a substantial quantity of olefins and of low sulfur content meeting commercial requirements. The finished gasoline likewise meets specifications for existent gum and the very low value for the copper dish gum test indicates an excellent gum stability. In the foregoing example, these substantial reductions in sulfur and gum bodies are effected without affecting the clear research octane number of the raw cracked gasoline.

Sulfur as thiophenes, reported herein, is determined by the Bureau of Mines procedure (R. I. 3591, December 1941). The olefin content of the raw cracked gasoline is determined by chromatographic adsorption analysis. However, the olefin content of the finished gasoline, from which thiophenes and other interferents have been substantially removed, is determined conventionally by the ASTM bromine number procedure (ASTM-D87546). Other analyses are obtained by use of conventional ASTM procedures, as indicated.

Similar results are obtained when the foregoing test is carried out with a catalyst carrying a promoter comprising other metallic elements of groups VA, VIA and VIII of the periodic table such as cobalt, vanadium, chromium, tungsten, platinum and nickel. The tungsten, platinum,

nickel and cobalt promoted catalysts are prepared by impregnation of the catalyst with aqueous solutions of salts of these metals, e. g., ammonium tungstate, platinic chloride, cobaltous nitrate or nickelic nitrate, whereas the chromium promoted catalyst is similarly prepared using chromic anhydride. The vanadium promoter is added by cooling 9, hot aqueou solution of ammonium meta-vanadate in which the catalyst has been suspended. Drying, calcination and sizing of these catalysts are conventionally effected.

In treating raw gasolines under the conditions of this invention, it has been observed that, in addition to removal of sulfur from raw cracked gasoline, the process is effective in removing amines, phenols, and like oxygen and nitrogen compounds which may likewise be present in such raw gasolines.

In view of the various modifications of the invention which will occur to those skilled in the art upon consideration of the foregoing disclosure without departing from the spirit or scope thereof, only such limitations should be imposed as are indicated by the appended claims.

What is claimed is:

1. A method of desulfurizing a highly olefinic hydrocarbon fraction, which comprises bringing hydrogen and a hydrocarbon fraction containing more than 1% by weight of sulfur in the form of cyclic sulfur compounds and a volume of olefins greater than the volume of paraffins and naphtheues therein, said volume of olefins being more than 20% by volume of said hydrocarbon fraction and imparting to said hydrocarbon fraction a high octane number into contact with a promoted siliceous catalyst consisting essentially of a major weight proportion of silica, a minor Weight proportion of at least one difiicultly reducible metal oxide and a catalyst promoter comprising an element selected from the class consisting of the metallic elements of groups VA, VIA and VIII of the periodic table in a reaction zone maintained at a temperature in the range of 775 to 925 F., the contact of said hydrogen and said hydrocarbon fraction resulting in a net consumption of hydrogen, passing said hydrocarbon fraction through the reaction zone at a space velocity in the range of about 0.5 to 5 liquid volumes per hour per volume of said promoted siliceous catalyst, maintaining the partial pressure of hydrogen in said reaction zone in the range of 20 to p. s. i., and recovering from the resulting reaction efiiuent a highly olefinic hydrocarbon fraction containing less than 0.3% by weight of sulfur and a major portion of said olefins and having a high octane number.

2. A method of desulfurizing a highly olefinic hydrocarbon fraction, which comprises bringing hydrogen and a hydrocarbon fraction containing more than 0.1% by weight of sulfur in the form of cyclic sulfur compounds and a volume of olefins greater than the volume of parafiins and naphthenes therein, said volume of olefins being more than 30% by volume of said hydrocarbon fraction and imparting to said hydrocarbon fraction a high octane number into contact with a promoted siliceous catalyst consisting essentially of a major weight proportion of silica, a minor weight proportion of at least one difiicultly reducible metal oxide and a catalyst promoter comprising an element selected from the class consisting of the metallic elements of groups VA, VIA and VIII of the periodic table in a reaction zone maintained at a temperature in the range of 800 to 900 F., the contact of said hydrogen and said hydrocarbon fraction resulting in a net consumption of hydrogen, passing said hydrocarbon fraction through the reaction zone at a space velocity in the range of about 0.5 to 5 liquid volumes per hour per volume of said promoted siliceous catalyst, maintaining the partial pressure of hydrogen in said reaction zone in the range of 20 to 100 p. s. i., and recovering from the resulting reaction efiluent a highly olefinic hydrocarbon fraction containing substantially less than L9 7 0.1% by weight of sulfur and a major portion of sai ole n an h vi eah s o an n mb A ethod of de fu i i a hi l n c as i e fraction, which comprises bringing hydrogen and. a gasoline fraction containing more than 1% .by weight of sulfur in the form of cyclic sulfurcompounds anda volume of olefins greater than the volume of paraflins and naphthenestherein, said .volume of olefins beingmore than 30% by volume of said gasoline fraction which ,has a clear research octane number of at least about 80 into contact with a promoted siliceous catalyst consisting essentially of a major weight proportion of silica, a minor weight proportion of at least one difiicultly reducible m tal xidean ic t qlys P t r comp g an ment selected from therclass consisting of the metallic elements of groups 'VA, VIA and 'VIII of the periodic table in a-.-reaction zone maintained at a temperature in the rangeof .=800 ..to.9.00 F., the contact of said hydrogen and saidgasolinefraction-resulting in a net consumption of :hydrogen, passing .said gasoline fraction through the reaction zone'at a-space velocity in the range of about 0.5 to 5 liquid volumes per hour per volume of said promoted-siliceous catalyst,.maintaining the partial pressure of hydrogen in said reaction zone in the-range of 20 to 100 -p. s. ..i., .and recovering :from the resulting reaction effluent a highly olefinic gasoline fractioncontaining less :than 0.3% by Weight of sulfur and amajor portion of said olefinsand havinga clear research octane number of at least aboutSO.

4. A methodaccordingto claim '3 wherein the catalyst promoter comprises molybdenum and the hydrogen partial pressure is in the range of 30 to 70 p. s. i.

5. A method of desulfurizing a highly olefinic gasoline fraction, which comprises bringing hydrogen and a gasoline fraction containing more than 0.3% by Weight of sulfur in the form of cyclic sulfur compounds and a volume of olefins greater than the volume of paraffins and naphthenes therein, said volume of olefins being more than 30% by volume of said gasoline fraction which has a clear research octane number of at least about 80 into contact with a promoted siliceous catalyst consisting essentially of a major weight proportion of silica, a minor weight proportion of at least one difficultly reducible metal oxide and a catalyst promoter comprising an element selected from the class consisting of the metallic elements of groups VA, VIA and VIII of the periodic table in a reaction zone maintained at a temperature in the range of 800 to 900 F., the contact of said hydrogen and said gasoline fraction resulting in a net consumption of hydrogen, passing said gasoline fraction through the reaction zone at a space velocity in the range of about 0.5 to 5 liquid volumes per hour per volume of said promoted siliceous catalyst, maintaining the partial pressure of hydrogen in said reaction zone in the range of 20 to 100 p. s. i., and recovering from the resulting reaction effluent a highly olefinic gasoline fraction containing less than 0.3% by weight of sulfur and a major portion of said olefins and having a clear research octane number of at least about 90.

6. A method of desulfurizing a highly olefinic gasoline fraction, which comprises bringing hydrogen and a gasoline fraction containing more than 0.1% by weight of sulfur in the form of cyclic sulfur compounds and a volume of olefins greater than the volume of paraffins and naphthenes therein, said volume of olefins being more than 20% by volume of said gasoline fraction and imparting to said gasoline fraction a high octane number into contact with a promoted siliceous catalyst consisting essentially of a major Weight proportion of silica, a minor Weight proportion of at least one difilcultly reducible metal oxide and a catalyst promoter comprising an element selected from the class consisting of the metallic elements of groups VA, VIA and VIII of the periodic table in a reaction zone maintained at a temperature in the range of 775 to 925 F., the contact of said hydrogen and said gasoline fraction resulting in a viiet consumption of hydrogen, passing said gasoline fraction through the reaction zone'at a space velocity the'range of about 0.5 to 5 liquid volumes ,per ,hour .per volume of said promoted siliceous catalyst, maintaining the partial pressure of hydrogen in said reaction zone in the range of 20 to 100 p. s. i., and recovering from the resulting reaction efllucnt a highly olefinic gasoline fraction containing substantially less than 0.1% by weight of sulfur and a major portion of said olefins and having a high octane number.

7. A-methodaccording to claim 6 wherein the promoted siliceous catalyst contains silica and alumina in the approximate weight ratio of 9: 1. I

8. A method according toclaim 7 wherein the catalyst promoter comprises molybdenum and the hydrogen partial pressureisin-the rangeof 30 to 70 p. s. i. i

9. A methodof desulfurizing a highly olefinic gasoline fraction, which comprises bringing hydrogen and a has a clear research octane number of at least about into contact with a-promoted siliceous catalyst consisting essentially ,Of a major weight proportion of silica, a minor weight proportion of at least .one diflicultly reducible metal oxide and acatalyst promoter comprisingan elernenhselected from the class consisting of the metallic elements ofgroups VA, VIA and VIII of the periodic table in a reaction zone maintained at a temperature in the range of 800 to 900 F., the contact of said hydrogen and said gasoline fraction resulting in a net consumption of hydrogen, passing said gasoline fraction through the reaction zone at a space velocity in the range of about 0.5 to 5 liquid volumes per hour per volume of said promoted siliceous catalyst, maintaining the partial pressure of hydrogen in said reaction zone in the range of 30 to 70 p. s. i., and recovering from the resulting reaction effluent a highly olefinic gasoline fraction containing substantially less than 0.1% by weight of sulfur and a major portion of said olefins and having a clear research octane number of at least about 80.

10. A method according to claim 9 wherein the catalyst promoter comprises molybdenum and the gasoline fraction passes through the reaction zone at a space velocity of 0.5 to 1.5 liquid volumes per hour per volume of said promoted siliceous catalyst.

11. A method of desulfurizing a highly olefinic gasoline fraction, which comprises bringing hydrogen and a gasoline fraction containing more than 0.1% by weight of sulfur in the form of cyclic sulfur compounds and a volume of olefins greater than the volume of paratfins and naphthenes therein, said volume of olefins being more than 30% by volume of said gasoline fraction which has a clear research octane number of at least about 80 into contact with a promoted siliceous catalyst consisting essentially of a major Weight proportion of silica, a minor Weight proportion of at least one difiicultly reducible metal oxide and a catalyst promoter comprising an element selected from the class consisting of the metallic elements of groups VA, VIA and VIII of the periodic table in a reaction zone maintained at a temperature in the range of 800 to 900 F., the contact of said hydrogen and said gasoline fraction resulting in a net consumption of hydrogen, passing said gasoline fraction through the reaction zone at a space velocity in the range of about 0.5 to 5 liquid volumes per hour per volume of said promoted siliceous catalyst, maintaining the partial pressure of hydrogen in said reaction zone in the range of 20 to p. s. i., and recovering from the resulting reaction efiluent a highly olefinic gasoline fraction con taining substantially less than 0.1% by weight of sulfur and a major portion of said olefins and having a clear research octane number of at least about 90.

12. A method according to claim 11 wherein the catalyst promoter comprises molybdenum and cobalt and the gasoline fraction passes through the reaction zone at a space velocity of 0.5 to 1.5 liquid volumes per hour per volume of said promoted siliceous catalyst.

13. A method of desulfurizing a highly olefinic gasoline, which comprises bringing hydrogen and a raw gasoline containing an appreciable quantity of troublesome foreign matter of the class of cyclic sulfur compounds and gum-forming bodies and containing a volume of olefins greater than the volume of parafiins and naphthenes therein, said volume of olefins being more than 20% by volume of said raw gasoline, which has a clear research octane number of at least about 80, into contact with a promoted siliceous catalyst consisting essentially of a major weight proportion of silica, a minor Weight proportion of at least one difiicultly reducible metal oxide and a catalyst promoter comprising a metallic element of group VIA of the periodic table in a reaction zone maintained at a temperature in the range of 800 to 900 F., the contact of said hydrogen and said raw gasoline resulting in a net consumption of hydrogen, passing said raw gasoline through the reaction zone at a space velocity in the range of about 0.5 to liquid volumes per hour per volume of said promoted siliceous catalyst, maintaining the partial pressure of hydrogen in said reaction zone in the range of 20 to 100 p. s. i., and recovering from the resulting reaction effluent a highly olefinic finished gasoline substantially free of troublesome foreign matter and containing at least 20% by volume of 12 said olefins and having a clear research octane number over 80.

14. A method according to claim 13 wherein the catalyst promoter comprises molybdenum and the hydrogen partial pressure is in the range of 30 to p. s. i.

15. A method according to claim 13 wherein the catalyst promoter comprises molybdenum and the raw gasoline passes through the reaction zone at a space velocity of 0.5 to 1.5 liquid volumes per hour per volume of said promoted siliceous catalyst.

16. A method according to claim 13 wherein the promoted siliceous catalyst is a promoted aluminum silicate.

References Cited in the file of this patent UNITED STATES PATENTS 2,079,359 Ocon May 4, 1937 2,340,922 Bent et al. Feb. 8, 1944 2,437,532 Huffman Mar. 9, 1948 2,486,361 Nahin et al. Oct. 25, 1949 2,500,146 Fleck et al. Mar. 14, 1950 2,560,433 Gilbert et al. July 10, 1951 2,646,388 Crawford July 21, 1953 2,647,076 Haresnape et al. July 28, 1953 2,687,370 Hendricks Aug. 24, 1954 2,695,866 McGrath Nov. 30, 1954 2,697,683 Engel et al. Dec. 21, 1954 OTHER REFERENCES Merrill: Rocks, Rock Weathering and Soils, page 

1. A METHOD OF DESULFURIZING A HIGHLY OLEFINIC HYDROCARBON FRACTION, WHICH COMPRISES BRINGING HYDROGEN AND A HYDROCARBON FRACTION CONTAINING MORE THAN 1% BY WEIGHT OF SULFUR IN THE FORM OF CYCLIC SULFUR COMPOUNDS, AND A VOLUME OF OLEFINS GREATER THAN THE VOLUME OF PARAFFINS AND NAPHTHENES THEREIN, SAID VOLUME OF OLEFINS BEING MORE THAN 20% BY VOLUME OF SAID HYDROCARBON FRACTION AND IMPARTING TO SAID HYDROCARBON FRACTION A HIGH OCTANE NUMBER INTO CONTACT WITH A PROMOTED SILICEOUS CATALYST CONSISTING ESSENTIALLY OF A MAJOR WEIGHT PROPORTION OF SILICA, A MINOR WEIGHT PROPORTION OF AT LEAST ONE DIFFICULTY REDUCIBLE METAL OXIDE AND A CATALYST PROMOTER COMPRISING AN ELEMENT SELECTED FROM THE CLASS CONSISTING OF THE METALLIC ELEMENTS OF GROUPS VA, VIA AND VIII OF THE PERIODIC TABLE IN A REACTION ZONE MAINTAINED AT A TEMPERATURE IN THE RANGE OF 775 TO 925* F., THE CONTACT OF SAID HYDROGEN AND SAID HYDROCARBON FRACTION RESULTING IN A NET CONSUMPTION OF HYDROGEN, PASSING SAID HYDROCARBON FRACTION THROUGH THE REACTION ZONE AT A SPACE VELOCITY IN THE RANGE OF ABOUT 0.5 TO 5 LIQUID VOLUMES PER HOUR PER VOLUME OF SAID PROMOTED SILICEOUS CATALYST, MAINTAINING THE PARTIAL PRESSURE OF HYDROGEN IN SAID REACTION ZONE IN THE RANGE OF 20 TO 100 P. S. I., AND RECOVERING FROM THE RESULTING REACTION EFFLUENT A HIGHLY OLEFINIC HYDROCARBON FRACTION CONTAINING LESS THAN 0.3% BY WEIGHT OF SULFUR AND A MAJOR PORTION OF SAID OLEFINS AND HAVING A HIGH OCTANE NUMBER. 